Scalable multifunctional MOFs-textiles via diazonium chemistry.

Cellulose fiber-based textiles are ubiquitous in daily life for their processability, biodegradability, and outstanding flexibility. Integrating cellulose textiles with functional coating materials can unlock their potential functionalities to engage diverse applications. Metal-organic frameworks (MOFs) are ideal candidate materials for such integration, thanks to their unique merits, such as large specific surface area, tunable pore size, and species diversity. However, achieving scalable fabrication of MOFs-textiles with high mechanical durability remains challenging. Here, we report a facile and scalable strategy for direct MOF growth on cotton fibers grafted via the diazonium chemistry. The as-prepared ZIF-67-Cotton textile (ZIF-67-CT) exhibits excellent ultraviolet (UV) resistance and organic contamination degradation via the peroxymonosulfate activation. The ZIF-67-CT is also used to encapsulate essential oils such as carvacrol to enable antibacterial activity against E. coli and S. aureus. Additionally, by directly tethering a hydrophobic molecular layer onto the MOF-coated surface, superhydrophobic ZIF-67-CT is achieved with excellent self-cleaning, antifouling, and oil-water separation performances. More importantly, the reported strategy is generic and applicable to other MOFs and cellulose fiber-based materials, and various large-scale multi-functional MOFs-textiles can be successfully manufactured, resulting in vast applications in wastewater purification, fragrance industry, and outdoor gears.

Reprogrammable, Sustainable, and 3D-Printable Cellulose Hydroplastic.

Modern human societies are highly dependent on plastic materials, however, the bulk of them are non-renewable commodity plastics that cause pollution problems and consume large amounts of energy for their thermal processing activities. In this article, a sustainable cellulose hydroplastic material and its composites, that can be shaped repeatedly into various 2D/3D geometries using just water are introduced. In the wet state, their high flexibility and ductility make it conducive for the shaping to take place. In the ambient environment, the wet hydroplastic transits spontaneously into rigid materials with its intended shape in a short time of <30 min despite a thickness of hundreds of microns. They also possess humidity resistance and are structurally stable in highly humid environments. Given their excellent mechanical properties, geometry reprogrammability, bio-based, and biodegradable nature, cellulose hydroplastic poses as a sustainable alternative to traditional plastic materials and even "green" thermoplastics. This article also demonstrates the possibility of 3D-printing these hydroplastics and the potential of employing them in electronics applications. The demonstrated hydroshapable structural electronic components show capability in performing electronic functions, load-bearing ability and geometry versatility, which are attractive features for lightweight, customizable and geometry-unique electronic devices.

Multifunctional Sandwich-Structured Super-Hygroscopic Zinc-Based MOF-Overlayed Cooling Wearables for Special Personal Thermal Management.

Personal protective equipment pays attention exclusively to external safety protection and ignores the internal thermoregulation of physiological state in association with sweating. Herein, a super-hygroscopic calcium-doped poly(sodium 4-styrenesulfonate) and superhydrophobic metal-organic-framework-overlayed wearables (Ca-PSS/MOF) integrated cooling wearable is proposed for special personal thermal management (PTM). Compared to the pristine fabric, the superhydrophobic MOF wearables exhibit anti-fouling and antibacterial capabilities, and the antibacterial efficiency is up to 99.99% and 98.99% against E. coli and S. aureus, respectively. More importantly, Ca-PSS/MOF demonstrate significant heat index changes up to 25.5 °C by reducing relative humidity dramatically from 91.0% to 60.0% and temperature from 36.5 to 31.6 °C during the running test. The practical feasibility of the Ca-PSS/MOF cooling wearables is well proved with the protective suit of the fireman. Owing to these multifunctional merits, the sandwich-structured cooling Ca-PSS/MOF are expected to provide new insights for designing the next-generation multifunctional apparel for PTM.

Protective effects of madecassoside, a triterpenoid from Centella asiatica, against oxidative stress in INS-1E cells.

Progressive decline in ß cell function and reduction in the ß cell mass is important in type 2 diabetes. Here, we tested the hypothesis that madecassoside's previously demonstrated in vivo protective effects on the ß cell in experimental diabetes were exerted directly. We investigated the effects of madecassoside in protecting a ß cell line (INS-1E) against a variety of agents. INS-1E cells were treated with madecassoside in the presence of high glucose (HG), a cytokine mixture, hydrogen peroxide (H2O2), or streptozotocin (STZ). HG, the cytokine mixture, H2O2 and STZ each produced a significant decrease in cell viability; this was significantly reversed by madecassoside. Pre-treatment with madecassoside reduced the number of apoptotic cells induced by HG, the cytokine mixture, H2O2, and STZ, and concentration-dependently reduced ROS production. Madecassoside also significantly enhanced glucose-induced insulin secretion. The results suggest that madecassoside's in vivo effects are exerted directly on the ß cell.

Autonomous Atmospheric Water Harvesting over a Wide RH Range Enabled by Super Hygroscopic Composite Aerogels.

Sorption-based atmospheric water harvesting (SAWH) offers a sustainable strategy to address the global freshwater shortage. However, obtaining sorbents with excellent performance over a wide relative humidity (RH) range and devices with fully autonomous water production remains challenging. Herein, magnesium chloride (MgCl2) is innovatively converted into super hygroscopic magnesium complexes(MC), which can effectively solve the problems of salt deliquescence and agglomeration. The MC are then integrated with photothermal aerogels composed of sodium alginate and carbon nanotubes (SA/CNTs) to form composite aerogels, which showed high water uptake over a wide RH range, reaching 5.43 and 0.27 kg kg-1 at 95% and 20% RH, respectively. The hierarchical porous structure enables the as-prepared SA/CNTs/MC to exhibit rapid absorption/desorption kinetics with 12 cycles per day at 70% RH, equivalent to a water yield of 10.0 L kg-1 day-1. To further realize continuous and practical freshwater production, a fully solar-driven autonomous atmospheric water generator is designed and constructed with two SA/CNTs/MC-based absorption layers, which can alternately conduct the water absorption/desorption process without any other energy consumption. The design provides a promising approach to achieving autonomous, high-performance, and scalable SAWH.

Biopolymers for Hygroscopic Material Development.

The effective management of atmospheric water will create huge value for mankind. Diversified and sustainable biopolymers that are derived from organisms provide rich building blocks for various hygroscopic materials. Here, a comprehensive review of recent advances in developing biopolymers for hygroscopic materials is provided. It is begun with a brief introduction of species diversity and the processes of obtaining various biopolymer materials from organisms. The fabrication of hygroscopic materials is then illustrated, with a specific focus on the use of biopolymer-derived materials as substrates to produce composites and the use of biopolymers as building blocks to fabricate composite gels. Next, the representative applications of biopolymer-derived hygroscopic materials for dehumidification, atmospheric water harvesting, and power generation are systematically presented. An outlook on future challenges and key issues worthy of attention are finally provided.

Effect of madecassoside in reducing oxidative stress and blood glucose in streptozotocin-nicotinamide-induced diabetes in rats.

OBJECTIVES: Madecassoside (MAD) is a triterpenoid constituent of Centella asiatica (L.) Urb., an ethnomedical tropical plant, extracts of which were shown to reduce blood glucose in experimental diabetes. This study examines MAD for its anti-hyperglycaemic effects and tests the hypothesis that it reduces the blood glucose in experimentally induced diabetic rats by protecting the ß-cells. METHODS: Diabetes was induced using streptozotocin (60 mg/kg, i.v.) followed by nicotinamide (210 mg/kg, intraperitoneal (i.p.)). MAD (50 mg/kg) was administered orally for 4 weeks, commencing 15 days after induction of diabetes; resveratrol (10 mg/kg) was used as a positive control. Fasting blood glucose, plasma insulin, HbA1c, liver and lipid parameters were measured, along with antioxidant enzymes and malondialdehyde as an index of lipid peroxidation; histological and immunohistochemical studies were also undertaken. KEY FINDINGS: MAD normalized the elevated fasting blood glucose levels. This was associated with increased plasma insulin concentrations. MAD alleviated oxidative stress by improving enzymatic antioxidants and reducing lipid peroxidation. Histopathological examination showed significant recovery of islet structural degeneration and an increased area of islets. Immunohistochemical staining showed increased insulin content in islets of MAD-treated rats. CONCLUSIONS: The results demonstrate an antidiabetic effect of MAD associated with preservation of ß-cell structure and function.

Wood Lamella-Inspired Photothermal Stearic Acid-Eutectic Gallium-Indium-Based Phase Change Aerogel for Thermal Management and Infrared Stealth.

Eutectic Gallium-Indium (EGaIn) liquid metal is an emerging phase change metal material, but its low phase transition enthalpy and low light absorption limit its application in photothermal phase change energy storage materials (PCMs) field. Here, based on the dipole layer mechanism, stearic acid (STA)-EGaIn-based PCMs which exhibit extraordinary solar-thermal performance and phase change enthalpy are fabricated by ball milling method. The wood lamella-inspired cellulose-derived aerogel and molybdenum disulfide (MoS2 ) are used to support the PCMs by the capillary force and decrease the interfacial thermal resistance. The resulted PCMs achieved excellent photothermal conversion performance and leakage proof. They  have excellent thermal conductivity of 0.31 W m-1 K-1 (this is increased by 138% as compared with pure STA), and high phase change enthalpy of187.50 J g-1 , which is higher than the most of the reported PCMs. Additionally, the thermal management system and infrared stealth materials based on the PCMs are developed. This work provides a new way to fabricate smart EGaIn-based PCMs for energy storage device thermal management and infrared stealth.

Ambient-conditions spinning of functional soft fibers via engineering molecular chain networks and phase separation.

Producing functional soft fibers via existing spinning methods is environmentally and economically costly due to the complexity of spinning equipment, involvement of copious solvents, intensive consumption of energy, and multi-step pre-/post-spinning treatments. We report a nonsolvent vapor-induced phase separation spinning approach under ambient conditions, which resembles the native spider silk fibrillation. It is enabled by the optimal rheological properties of dopes via engineering silver-coordinated molecular chain interactions and autonomous phase transition due to the nonsolvent vapor-induced phase separation effect. Fiber fibrillation under ambient conditions using a polyacrylonitrile-silver ion dope is demonstrated, along with detailed elucidations on tuning dope spinnability through rheological analysis. The obtained fibers are mechanically soft, stretchable, and electrically conductive, benefiting from elastic molecular chain networks via silver-based coordination complexes and in-situ reduced silver nanoparticles. Particularly, these fibers can be configured as wearable electronics for self-sensing and self-powering applications. Our ambient-conditions spinning approach provides a platform to create functional soft fibers with unified mechanical and electrical properties at a two-to-three order of magnitude less energy cost under ambient conditions.

All-Day Multicyclic Atmospheric Water Harvesting Enabled by Polyelectrolyte Hydrogel with Hybrid Desorption Mode.

Sorption-based atmospheric water harvesting (AWH) is a promising approach for mitigating worldwide water scarcity. However, reliable water supply driven by sustainable energy regardless of diurnal variation and weather remains a long-standing challenge. To address this issue, a polyelectrolyte hydrogel sorbent with an optimal hybrid-desorption multicyclic-operation strategy is proposed, achieving all-day AWH and a significant increase in daily water production. The polyelectrolyte hydrogel possesses a large interior osmotic pressure of 659 atm, which refreshes sorption sites by continuously migrating the sorbed water within its interior, and thus enhancing sorption kinetics. The charged polymeric chains coordinate with hygroscopic salt ions, anchoring the salts and preventing agglomeration and leakage, thereby enhancing cyclic stability. The hybrid desorption mode, which couples solar energy and simulated waste heat, introduces a uniform and adjustable sorbent temperature for achieving all-day ultrafast water release. With rapid sorption-desorption kinetics, an optimization model suggests that eight moisture capture-release cycles are capable of achieving high water yield of 2410 mLwater kgsorbent -1 day-1 , up to 3.5 times that of single-cyclic non-hybrid modes. The polyelectrolyte hydrogel sorbent and the coupling with sustainable energy driven desorption mode pave the way for the next-generation AWH systems, significantly bringing freshwater on a multi-kilogram scale closer.

In Situ Grown Silver-Polymer Framework with Coordination Complexes for Functional Artificial Tissues.

Self-sensing actuators are critical to artificial robots with biomimetic proprio-/exteroception properties of biological neuromuscular systems. Existing add-on approaches, which physically blend heterogeneous sensor/actuator components, fall short of yielding satisfactory solutions, considering their suboptimal interfaces, poor adhesion, and electronic/mechanical property mismatches. Here, a single homogeneous material platform is reported by creating a silver-polymer framework (SPF), thus realizing the seamless sensing-actuation unification. The SPF-enabled elastomer is highly stretchable (1200%), conductive (0.076 S m-1 ), and strong (0.76 MPa in-strength), where the stretchable polymer matrix synthesis and in situ silver nanoparticles reduction are accomplished simultaneously. Benefiting from the multimodal sensing capability from its architecture itself (mechanical and thermal cues), self-sensing actuation (proprio-deformations and external stimuli perceptions) is achieved for the SPF-based pneumatic actuator, alongside an excellent load-lifting attribute (up to 3700 times its own weight), substantiating its advantage of the unified sensing-actuation feature in a single homogenous material. In view of its human somatosensitive muscular systems imitative functionality, the reported SPF bodes well for use with next-generation functional tissues, including artificial skins, human-machine interfaces, self-sensing robots, and otherwise dynamic materials.

Hygrothermic Wood Actuated Robotic Hand.

Stimulus-responsive actuators play a vital role in the new generation of intelligent systems. However, poor mechanical performance, complicated fabrication processes, and the inability to complex deformation limit their practical applications. Herein, these challenges are overcome via designing a strong hygrothermic wood actuator with asymmetric water affinity. The actuator is readily constructed by sandwiching polypyrrole-coated wood with a Ni complex hygroscopic gel top layer for moisture absorption and a polyimide bottom layer as the water barrier. The resulting hygrothermic wood spontaneously stretches and bends itself in response to moisture and thermal/light stimulation. A robotic hand and a series of grippers made of hygrothermic wood demonstrate dexterous object-hand interactions during grasping and holding, while the reversible hygrothermic property allows the actuator to be potentially applied in fire rescue scenarios to rescue trapped objects. A combination of good mechanical properties, multi-stimulus-response, complex deformation, wide working temperature range, low manufacturing cost, and biocompatibility are simultaneously realized by one device. It is thus believed that such a strong wood actuator will open up a new avenue for building intelligent robotic hand systems.

Self-Sustained Programmable Hygroelectronic Interfaces for Humidity-Regulated Hierarchical Information Encryption and Display.

The emerging moisture-driven energy generation (MEG) technology opens up new possibilities for humidity-responsive materials, devices, and interdisciplinary opportunities in fields like information security. However, such potential remains untapped. Here, an original MEG structure with a hygroionic energy-conversion route by selective coating of ionic hygroscopic hydrogels on a carbon black surface is reported. The hygroionic route features a process in which the scavenged energy is stored in the electrical double layers formed at the interfaces between the ionic hydrogel and the carbon nanoparticles. The resultant electrical field developed across the hydrogel-coated wet carbon and the rest of the dry carbon area is thus durably lasted. Based on this unique structure, hygroelectronic information interfaces (HEII) for humidity-regulated information encryption and display are put forward by devising hydrogel patterns on a carbon platform. Further by tuning the hygroscopicity of the ionic hydrogels and incorporating encoding methods (e.g., Morse code), it is demonstrated that the HEII platform is programmable to carry different information in certain humidity ranges. Unlike those conventional anti-counterfeiting methods that optically reveal the hidden information once the required stimulus is provided, the new HEII serves as a hierarchical solution for high-security encryption and display.

In Situ Growth of a Stable Metal-Organic Framework (MOF) on Flexible Fabric via a Layer-by-Layer Strategy for Versatile Applications.

Fabrics have been used broadly in daily life for an enormous variety of applications due to their intrinsic advantages, such as flexibility, renewability, and good processability. Integrating natural fabrics with metal-organic frameworks (MOFs) is an effective strategy to improve the added value of textiles with special functionalities. Here, a facile, low-cost, and scalable technology is reported for the in situ growth of MOFs on cotton fabrics. A uniform and dense coating of regular octahedral Cu-1,3,5-benzenetricarboxylic acid (CuBTC) crystals was formed on the fiber surface, followed by treatment with 1H,1H,2H,2H-perfluorooctyltriethoxysilane and triethoxyoctylsilane to create a superhydrophobic CuBTC@cotton fabric (SMCF), which greatly improved its water stability and extended superhydrophobic CuBTC's potential applications. The as-prepared MCF has a specific surface area of 229 m2/g, which is 11 times that of pristine fabrics (21 m2/g). This high porosity further endows the fabric with enhanced loading capacity of essential oils to enable excellent antibacterial ability. Moreover, the SMCF also exhibits excellent self-cleaning, UV shielding, and anti-icing performances. In addition, we performed COMSOL simulations to investigate the dynamic freezing process of water on the surface of samples, which agrees well with our experimental observations. By combining the merits of both fabrics and MOFs, the MCF is expected to extend the applications of traditional textiles in antifouling, safety, the fragrance industry, and healthcare for the next-generation multifunctional fabrics.

An Asymmetric Hygroscopic Structure for Moisture-Driven Hygro-Ionic Electricity Generation and Storage.

The interactions between moisture and materials give rise to the possibility of moisture-driven energy generation (MEG). Current MEG materials and devices only establish this interaction during water sorption in specific configurations, and conversion is eventually ceased by saturated water uptake. This paper reports an asymmetric hygroscopic structure (AHS) that simultaneously achieves energy harvesting and storage from moisture absorption. The AHS is constructed by the asymmetric deposition of a hygroscopic ionic hydrogel over a layer of functionalized carbon. Water absorbed from the air creates wet-dry asymmetry across the AHS and hence an in-plane electric field. The asymmetry can be perpetually maintained even after saturated water absorption. The absorbed water triggers the spontaneous development of an electrical double layer (EDL) over the carbon surface, which is termed a hygro-ionic process, accounting for the capacitive properties of the AHS. A peak power density of 70 µW cm-3  was realized after geometry optimization. The AHS shows the ability to be recharged either by itself owing to a self-regeneration effect or via external electrical means, which allows it to serve as an energy storage device. In addition to insights into moisture-material interaction, AHSs further shows potential for electronics powering in assembled devices.

Reversible Hydration Composite Films for Evaporative Perspiration Control and Heat Stress Management.

Donning of personal protective equipment (PPE) in the healthcare sector has been intensified by the on-going COVID-19 pandemic around the globe. While extensive PPE provides protection, it typically limits moisture permeability and severely hinders the sweat evaporation process, resulting in greater heat stress on the personnel. Herein, a zinc-poly(vinyl alcohol) (Zn-PVA) composite film is fabricated by embedding a super-hygroscopic zinc-ethanolamine complex (Zn-complex) in the PVA matrix. By attaching the Zn-PVA composite film, the relative humidity (RH) inside the protective suit decreases from 91.0% to 48.2%. The reduced RH level, in turn, enhances evaporative cooling, hence bringing down the heat index from 64.6 to 40.0 °C at an air temperature of 35 °C, remarkably lowering the likelihood of heat stroke. The American Society for Testing and Materials tests conducted on a sweating manikin have also proven that the Zn-PVA composite films can significantly reduce the evaporative resistance of the protective suit by 90%. The low material cost, facile fabrication process, and reusability allow the Zn-PVA composition films to be readily available for healthcare workers worldwide. This application can be further extended to other occupations that are facing severe thermal discomfort and heat stress.

Plasmonic protein electricity generator.

Interest in acquiring green energy from sunlight is driving research into the incorporation of biological photosynthetic materials into biohybrid devices. A potential way to enhance solar energy conversion by photosynthetic proteins is to couple them to plasmonic nanomaterials to enhance absorption of incident radiation. In this work, a variety of plasmonic nanoparticles were used to boost the photocurrent output of a Protein Electricity Generator (PEG). Mixing gold nanoparticles (NPs) of five different architectures into the photoprotein/electrolyte contents of the cell was found to increase device performance, the most effective being ∼120 nm diameter star-shaped clusters that caused a ∼six-fold increase in photocurrent at the optimum dopant level. In addition, high-resolution electrohydrodynamic printing was used to create parallel line and square lattice patterns of silver nanoparticle ink on the tungsten rear electrode of the cells. Patterns with a 700 nm spacing between lines boosted photocurrents by up to three-fold and the effects of the gold and silver nanoparticles were additive, such that the ideal combination produced a ∼19-fold increase in photocurrent and device efficiency. We attribute the elevated performance to plasmonic enhancement of absorbance and scattering effects that increase the path length for photons in the device. Use of rear electrodes with silver nanoparticle lines and grids at 1100 nm spacing did not increase photocurrents, highlighting the importance of precision printing of nanostructures for the enhancement of device performance.

Solar-Driven Gas-Phase Moisture to Hydrogen with Zero Bias.

Band structure engineering offers a perfect route to tune the transport properties of electrons and holes independently, especially in semiconductors for water splitting. Here, we explore the possibility of achieving a bias-free single-step solar to chemical energy conversion using gas-phase moisture as the reactant while generating hydrogen as the reaction product. A metal-based superhygroscopic hydrogel scavenges moisture from the ambient environment and serves as the water source. The FeOOH/BiVO4 heterojunction works as the photoanode wherein the interface allows the transport of electrons to the outer layer, resulting in an upward band bending. Concomitantly, the negative charges will accumulate on the Cu2O surface in the FeOOH/Cu2O photocathode, inducing a downward band bending. With the use of the hydrogel, photoanode, and photocathode, a device for directly splitting the moisture absorbed from the ambient air is realized, generating a photocurrent of 0.75 mA cm-2 under the one-sun intensity of cool daylight without any additional bias. The solar-cell-assisted device can split 6 mg of moisture in 10 h, and the hydrogel can absorb more than 30 mg of moisture in the same period.

Near-Instantaneously Self-Healing Coating toward Stable and Durable Electromagnetic Interference Shielding.

Durable electromagnetic interference (EMI) shielding is highly desired, as electromagnetic pollution is a great concern for electronics' stable performance and human health. Although a superhydrophobic surface can extend the service lifespan of EMI shielding materials, degradation of its protection capability and insufficient self-healing are troublesome issues due to unavoidable physical/chemical damages under long-term application conditions. Here, we report, for the first time, an instantaneously self-healing approach via microwave heating to achieve durable shielding performance. First, a hydrophobic 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) layer was coated on a polypyrrole (PPy)-modified fabric (PPy@POTS), enabling protection against the invasion of water, salt solution, and corrosive acidic and basic solutions. Moreover, after being damaged, the POTS layer can, for the first time, be instantaneously self-healed via microwave heating for a very short time, i.e., 4 s, benefiting from the intense thermal energy generated by PPy under electromagnetic wave radiation. This self-healing ability is also repeatable even after intentionally severe plasma etching, which highlights the great potential to achieve robust and durable EMI shielding applications. Significantly, this approach can be extended to other EMI shielding materials where heat is a triggering stimulus for healing thin protection layers. We envision that this work could provide insights into fabricating EMI shielding materials with durable performance for portable and wearable devices, as well as for human health care.